Process for the manufacture of unsaturated aldehydes and acids from the corresponding olefins

ABSTRACT

A process for the catalytic oxidation of olefins to unsaturated aldehydes and acids and the ammoxidation of olefins to unsaturated nitriles in which the catalyst comprises a promoted, reduced, antimony oxidemolybdenum oxide-containing catalyst.

This is a division of application Ser. No. 224,967, filed Feb. 9, 1972,now U.S. Pat. No. 3,892,794.

This invention relates to a process for the catalytic oxidation ofolefins to unsaturated aldehydes and acids and to the oxidation ofolefin-ammonia mixtures to unsaturated nitriles. More specifically thisinvention relates to a process for the catalytic oxidation of olefinssuch as propylene and isobutylene to acrolein, acrylic acid,methacrolein, and methacrylic acid, respectively, and the ammoxidationof propylene and isobutylene, respectively, to acrylonitrile andmethacrylonitrile.

The catalyst of this invention is composed of the oxides of molybdenumand antimony and preferably contains other metal oxides. The catalystcompositions most useful in this invention are represented by thefollowing formula:

    A.sub.a B.sub.b Sb.sub.c Mo.sub.d O.sub.e

wherein A comprises one or more of the promoting elements selected fromthe group consisting of tellurium, tungsten, titanium, manganese,nickel, iron, copper, lead, rhenium, bismuth, tin, uranium, chromium,phosphorus and boron, and B is a member selected from the groupconsisting of molybdenum, tungsten, aluminum, nickel and sulfur, andwherein a is a number of from 0.001 to 1.0, b is a number of from 0 to2.0 c is a number from 1 to 9, d is a number from 1 to 9, and e is anumber dependent upon the valence requirements of the combined metals.The preferred catalysts include those compositions wherein a is 0.005 to0.5, b is 0.001 to 1.0, c is 1 to 8, d is 1 to 8 and e is 4 to 40.

The method employed in preparing the catalyst of this invention iscritical to the oxidation process described herein. In the empiricalformula designating the composition of the catalyst of this invention, Ain the formula represents a promoter element and B represents a reducingelement. The method employed in preparing the catalyst departs from theusual classical procedures involving co-precipitation or impregnationtechniques and involves the simple mixing of the respective metal oxidesof antimony and molybdenum, the reducing agent and the compound of thepromoter element or elements as a slurry in water.

In a preferred procedure for combining the essential elements of thecatalyst composition, an aqueous suspension of molybdenum trioxide ispre-reduced in a controlled manner so that at least some of themolybdenum is reduced to a valence state below +6 before the molybdenumoxide is mixed with a lower oxide of antimony, antimony trioxide. A widerange of reducing agents can be employed for this purpose includingfinely divided or colloidal metals such as molybdenum, tungsten,magnesium, aluminum, nickel, bismuth, antimony, chromium, cobalt, zinc,cadmium, tin, or iron, sulfur, hydrogen sulfide, sulfur dioxide,hydrazine hydrate, ammonia, hydroxylamine, organic reducing agents, suchas, sugars, pyrogallol, and the like. Most preferred is finely dividedmetal in the amount of from about 0.01 to 0.2 atoms of metal per mole ofmolybdenum trioxide present. It is also preferred that the promoterelement be added in a non-oxidizing form.

On refluxing the aqueous suspension of molybdenum trioxide with thereducing agent, at least a part of the normally insoluble molybdenumtrioxide is solublized forming an intense deep blue coloration. It ishypothesized that this blue color which develops is the result of thereduction of molybdenum, at least in part, to a lower oxidation state inthe oxidation-reduction reaction occurring between hexavalent molybdenumand the reducing metal. Although preferredly the molybdenum trioxide ispre-reduced before reaction with the antimony trioxide, beneficialresults are also obtained by first reacting the molybdenum trioxide withantimony trioxide followed by reaction with the reducing agent, or byreacting the three components simultaneously. It is also contemplated tobe within the scope of this invention to employ a combination of a loweroxide of molybdenum with a higher oxide of antimony, as for exampleantimony tetroxide or antimony pentoxide in preparation of the catalyst.

Preferredly, the metal promoter of the catalyst is subsequently added tothe aqueous suspension of mixed oxides of antimony, molybdenum and thereducing metal, in the form of a non-oxidizing compound such as, forexample, the metal oxide, hydrous metal oxide, the hydroxide, thehalide, the acid, a salt of the acid, a salt of an organic acid, anorganometallic compound and the like. Satisfactory results are alsoobtained, however, by adding the promoter element to the componentmixture at any stage of the catalyst preparation.

A highly reproducible method for combining the components of thecatalyst of this invention comprises refluxing an aqueous suspension ofmolybdenum trioxide and a finely divided metal for a period of about 1to 3 hours at 100° C. until the deep blue coloration characteristic of alower oxidation state of molybdenum appears. Antimony trioxide is thenadded to the aqueous suspension of the reduced molybdenum oxide and thereducing metal and this mixture is again refluxed at 100° C. for aperiod of about 1 to 5 hours. To this mixture is added the metalpromoter in a form disclosed hereinabove, and the entire mixture isfurther refluxed for about 1 to 5 hours at the same temperature. Theaqueous slurry is then evaporated to dryness, and final drying isaccomplished by placing the catalyst in an oven at a temperature ofabout 120° to 130° C. for a period of from about 2 to 24 hours.

The catalyst of this invention may be supported on a carrier materialsuch as for example, silica, zirconia, calcium stabilized-zirconia,titanis, alumina, thoria, silicon carbide, clay, pumice, diatomaceousearth and the like, or it may be employed satisfactorily in anunsupported form. If a carrier is utilized it may be employed in amountsof up to 95 percent by weight of the total catalyst composition.

The catalyst system herein described is useful in the oxidation ofolefins to corresponding oxygenated compounds, such as unsaturatedaldehydes and acids, and in the ammoxidation of olefins to unsaturatednitriles. Nitriles and oxygenated compounds such as aldehydes and acidscan be produced simultaneously using process conditions within theoverlapping ranges for these reactions, as set forth in detail below.The relative proportions of each that are obtainable will depend on thecatalyst and on the olefin employed. It is also contemplated to bewithin the scope of this invention, that with the catalyst systememployed herein, the unsaturated aldehyde may be further oxidized in asecond step to the corresponding unsaturated acid. The unsaturatedaldehyde need not be isolated from the other reaction products and canbe further oxidized to the unsaturated acid while remaining in thereaction mixture. The term "oxidation" as used in this specification andclaims encompasses the oxidation to aldehydes and acids and to nitriles,all of which conversions require oxygen as a reactant.

Oxidation of Olefins to Aldehydes and Acids

The reactants used in the oxidation to obtain oxygenated compounds areoxygen and an olefin such as propylene or isobutylene, or theirmixtures.

The olefins may be in admixture with paraffinic hydrocarbons, such asethane, propane, butane and pentane, as for example, a propylene-propanemixture may constitute the feed. This makes it possible to use ordinaryrefinery streams without special preparation.

The temperature at which this oxidation is conducted may varyconsiderably depending upon the catalyst, the particular olefin beingoxidized and the correlated conditions of the rate of throughput orcontact time and the ratio of olefin to oxygen. In general, whenoperating at pressures near atmospheric, i.e., --10 to 100 p.s.i.g.,temperatures in the range of 250° to 600° C. may be advantageouslyemployed. However, the process may be conducted at other pressures, andin the case where superatmospheric pressures, e.g., above 100 p.s.i.g.are employed somewhat lower temperatures are feasible. In the case wherethis process is employed to convert propylene to acrolein and acrylicacid, or isobutylene to methacrolein and methacrylic acid, a temperaturerange of from about 300° to 500° C. has been found to be optimum atatmospheric pressure.

While pressures other than atmospheric may be employed it is generallypreferred to operate at or near atmospheric pressure, since the reactionproceeds well at such pressures and the use of expensive high pressureequipment is avoided. Pressures of between atmospheric and 30 p.s.i.g.are most preferred.

The apparent contact time employed in the process is not critical andmay be selected from a broad operable range which may vary from 0.1 to50 seconds. The apparent contact time may be defined as the length oftime in seconds which the unit volume of gas measured under theconditions of reaction is in contact with the apparent unit volume ofthe catalyst. It may be calculated, for example, from the apparentvolume of the catalyst bed, the average temperature and pressure of thereactor, and the flow rates of the several components of the reactionmixture.

The optimum contact time will, of course, vary depending upon the olefinbeing treated, but in the case of propylene and isobutylene thepreferred apparent contact time is 0.5 to 15 seconds.

A molar ratio of oxygen to olefin between about 0.5:1 to 10:1 generallygives the most satisfactory results. For the conversion of propylene toacrolein, and isobutylene to methacrolein and methacrylic acid, apreferred ratio of oxygen to olefin is from about 1:1 to about 5:1. Theoxygen used in the process may be derived from any source; however, airis the least expensive source of oxygen, and is preferred.

The addition of water to the reaction mixture has a marked beneficialinfluence on the course of the reaction in that it improves theconversion and the yield of the desired product. Accordingly, we preferto include water in the reaction mixture. Generally, a ratio of olefinto water in the reaction mixture of from 1:0.5 to 1:10 will give verysatisfactory results, and a ratio of from 1:1 to 1:6 has been found tobe optimum when converting propylene to acrolein and acrylic acid, andisobutylene to methacrolein and methacrylic acid. The water, of course,will be in the vapor phase during the reaction.

Inert diluents such as nitrogen and carbon dioxide may be present in thereaction mixture.

Oxidation of Olefins to Nitriles

The reactants used are the same as those employed in the production ofaldehydes and acids above, plus ammonia. Any of the olefins describedcan be used.

In its preferred aspect, the process comprises contacting a mixturecomprising propylene or isobutylene, ammonia and oxygen with thecatalyst at an elevated temperature and at atmospheric or nearatmospheric pressure.

Any source of oxygen may be employed in this process. For economicreasons, however, it is preferred that air be employed as the source ofoxygen. From a purely technical viewpoint, relatively pure molecularoxygen will give equivalent results. The molar ratio of oxygen to theolefin in the feed to the reaction vessel should be in the range of0.5:1 to 10:1 and a ratio of about 1:1 to 5:1 is preferred.

Low molecular weight saturated hydrocarbons do not appear to influencethe reaction to an appreciable degree, and these materials can bepresent. Consequently, the addition of saturated hydrocarbons to thefeed to the reaction is contemplated within the scope of this invention.Similarly diluents such as nitrogen and the oxides of carbon may bepresent in the reaction mixture without deleterous effect.

The molar ratio of ammonia to olefin in the feed to the reaction mayvary between about 0.05:1 to 5:1. There is no real upper limit for theammonia-olefin ratio, but there is generally no reason to exceed the 5:1ratio. At ammonia-olefin ratios appreciably less than the stoichiometricratio of 1:1, various amounts of oxygenated derivates of the olefin willbe formed.

Significant amounts of unsaturated aldehydes and even unsaturated acidsas well as nitriles will be obtained at ammonia-olefin ratiossubstantially below 1:1, i.e., in the range of 0.15:1 to 0.75:1,particularly in the case of higher olefins such as isobutylene. Outsidethe upper limit of this range only insignificant amounts of aldehydesand acids will be produced, and only small amounts of nitriles will beproduced at ammonia-olefin ratios below the lower limit of this range.It is generally possible to recycle any unreacted olefin and unconvertedammonia.

We have found that in many cases water in the mixture fed to thereaction vessel improves the selectivity of the reaction and yield ofnitrile. However, reactions not including water in the feed are not tobe excluded from this invention, inasmuch as water is formed in thecourse of the reaction. Sometimes it is desirable to add some water tothe reaction mixture, and in general, molar ratios of added water toolefin, when water is added, on the order of 1:1 to 4:1 are particularlydesirable. However higher ratios may be employed, i.e., ratios of up toabout 10:1 are feasible.

The reaction is carried out at a temperature within the range from about250° to about 600° C. The preferred temperature range is from about 350°to 500° C.

The pressure at which the reaction is conducted is not critical, and thereaction should be carried out at about atmospheric pressure orpressures up to about 5 atmospheres. In general, high pressures, i.e.about 15 atmospheres, are not suitable, since higher pressures tend tofavor the formation of undesirable by-products.

The apparent contact time is an important variable, and contact time inthe range of from 0.1 to about 50 seconds may be employed. The optimumcontact time will, of course, vary, depending upon the olefin beingtreated, but in general, a contact time of from 1 to 15 seconds ispreferred.

In general, any apparatus of the type suitable for carrying outoxidation reactions in the vapor phase may be employed in the executionof this process. The processes may be conducted either continuously orintermittently. The catalyst bed may be a fixed bed employing a largeparticulate or pelleted catalyst, or in the alternative, a so-called"fluidized" bed of catalyst may be employed.

The reactor may be brought to the reaction temperature before or afterthe introduction of the reaction feed mixture. However, in a large scaleoperation, it is preferred to carry out the process in a continuousmanner, and in such a system the recirculation of the unreacted olefinis contemplated. Periodic regeneration or reactivation of the catalystis also contemplated, and this may be accomplished, for example, bycontacting the catalyst with air at an elevated temperature.

The products of the reaction may be recovered by any of the methodsknown to those skilled in the art. One such method involves scrubbingthe effluent gases from the reactor with cold water or an appropriatesolvent to remove the products of the reaction. In the recovery ofnitrile products it may be desirable to employ acidified water to absorbthe products reaction and neutralize unconverted ammonia. The ultimaterecovery of the products may be accomplished by conventional means, suchas by distillation or solvent extraction. The efficiency of thescrubbing operation may be improved when water is employed as thescrubbing agent by adding a suitable wetting agent to the water. Wheremolecular oxygen is employed as the oxidizing agent in this process, theresulting product mixture remaining after the removal of the aldehydes,acids and nitriles may be treated to remove carbon dioxide with theremainder of the mixture containing the unreacted olefin and oxygenbeing recycled through the reactor. In the case where air is employed asthe oxidizing agent in lieu of molecular oxygen, the residual productafter separation of the nitriles and other carbonyl products may bescrubbed with a non-polar solvent, e.g., a hydrocarbon fraction, inorder to recover unreacted olefin, and in this case the remaining gasesmay be discarded. The addition of a suitable inhibitor to preventpolymerization of the unsaturated products during the recovery steps isalso contemplated.

The following examples are representative of the process conditions andcatalyst compositions that are suitable for the process of thisinvention, however, the scope of the invention is not to be limited bythese examples.

In the examples, the activity of the catalysts was determined using afixed-bed microreactor composed of a feed induction system, a moltensalt bath furnace, a scrubber and a vapor phase chromatograph. Thereactor was constructed from a 5 inches length of pipe having a 3/8 inchI.D., and a catalyst capacity of approximately 4 cc of catalyst.

The catalyst employed had a particle size of 20-32 mesh. The reactionproduct obtained from the oxidation reaction was absorbed in a waterscrubber and the ammoxidation product was absorbed in awater-hydrochloric acid scrubber solution. An aliquot of the scrubberliquid was subsequently injected into a Hewlett and Packard gaschromatograph Model No. 5750 for analysis. The chromatograph contained aPorapak-Q column, 2 meters in length and 1/8 inch in diameter.

The column was maintained at a temperature of 180° C. for the analysisof acrolein, methacrolein, acrylonitrile, methacrylonitrile and aceticacid, and at 230° C. for the analysis of acrylic acid and methacrylicacid. The unabsorbed gaseous product, consisting essentially of carbonmonoxide, carbon dioxide, oxygen, nitrogen and unreacted hydrocarbon,was analyzed by means of a Fisher Gas Partitioner. Hydrogen cyanide andammonia when present were determined by titration.

The reaction conditions employed and the conversions obtained utilizingthe various hydrocarbon feeds and catalyst compositions described in theinvention are summarized in Tables 1 to 5. In these experiments, theresults are reported as the mole percent per pass conversion to thedesired product which is defined as: ##EQU1## and selectivity on a molarbasis is defined as: ##EQU2##

The catalysts employed in Examples 1 to 40 (Tables 2 to 5) were preparedaccording to the following procedures:

EXAMPLE 1

64.8 Grams of molybdenum trioxide (MoO₃) (0.45 gram atoms of Mo) wasslurried in water and heated at 100° C. for one hour. 43.7 Grams ofantimony trioxide (Sb₂ O₃) (0.3 gram atoms of Sb) was added to theaqueous slurry and refluxing was continued for five hours at 110° C.This was then stirred constantly at room temperature for 16 hours. Thebulk of the slurry was then slowly evaporated to dryness, and the solidwas then dried at 130° C. for 40 hours.

EXAMPLE 2

64.8 Grams of molybdenum trioxide (MoO₃) (0.45 gram atoms of Mo) werereacted with 0.864 grams of molybdenum metal powder (0.009 gram atoms ofMo) in about 300 cc of water. The aqueous slurry was refluxed for aboutone hour with constant stirring. The color of the slurry on completionof the reaction was blue. To this slurry was added 43.7 grams ofantimony trioxide (Sb₂ O₃) (0.3 gram atoms of Sb), and stirring atreflux temperatures was continued at least for one additional hour. Thecolor of the slurry was dark green.

The promoted catalysts were prepared by adding the promoter element tothe slurry of Example 2 in the form of the compound and the amount ofthe compound indicated in Table I. The slurry containing the addedpromoter element was refluxed for 3 more hours with continual stirring,was then placed in a large beaker and was slowly evaporated to drynessover a hot plate. The solid was finally dried in an oven at 130° C. forabout 24 hours.

                                      TABLE I                                     __________________________________________________________________________         Reducing Element                                                         Example                                                                            in place of Mo°                                                                (grams)                                                                            Promoter Element                                                                        Grams of Compound Used                            __________________________________________________________________________    3    Al.sub.0.06                                                                           0.243                                                                              --                                                          4    Ni.sub.0.06                                                                           0.528                                                                              --                                                          5    S.sub.0.06                                                                            0.289                                                                              --                                                          6    W.sub.0.06                                                                            1.655                                                                              --                                                          7    Mo.sub.0.06                                                                           0.864                                                                              Bi.sub.0.01                                                                             0.727 Bi(NO.sub.2).sub.2.5H.sub.2 O +                                         HNO.sub.3                                         8    "       "    Bi.sub.0.1                                                                              6.61 Bi(C.sub.2 H.sub.3).sub.3                    9    "       "    Bi.sub.0.1                                                                              7.27 Bi(NO.sub.3).sub.2.5H.sub.2 O                10   "       "    P.sub.0.01                                                                              0.173 H.sub.3 PO.sub.4 (85% soln.)                11   "       "    P.sub.0.1 1.73 H.sub.3 PO.sub.4 (85% soln.)                 12   "       "    P.sub.0.21                                                                              4.325 H.sub.3 PO.sub.4 (85% soln.)                13   "       "    P.sub.0.5 8.647 H.sub.3 PO.sub.4 (85% soln.)                14   "       "    P.sub.1.0 17.299 H.sub.3 PO.sub.4 (85% soln.)               15   "       "    B.sub.0.01                                                                              0.093 H.sub.3 BO.sub.3                            16   "       "    Te.sub.0.01                                                                             0.404 TeCl.sub.4                                  17   "       "    Te.sub.0.1                                                                              4.041 TeCl.sub.4                                  18   W.sub.0.06                                                                            1.655                                                                              Te.sub.0.1                                                                              4.041 TeCl.sub.4                                  19   W.sub.0.2                                                                             5.52 Te.sub.0.1                                                                              4.041 TeCl.sub.4                                  20   Mo.sub.0.06                                                                           0.864                                                                              W.sub.0.1 3.75 H.sub.2 WO.sub.4                             21   "       "    Mn.sub.0.1                                                                              1.726 MnCO.sub.2                                  22   "       "    Ni.sub.0.1                                                                              1.781 NiCO.sub.2                                  23   "       "    Cu.sub.0.1                                                                              2.02 CuCl.sub.2                                   24   "       "    Pb.sub.0.1                                                                              5.69 Pb(C.sub.2 H.sub.3 O.sub.2).sub.2.3H.sub.                                2 O                                               25   "       "    Re.sub.0.1                                                                              4.02 NH.sub.4 ReO.sub.4                           26   "       "    Sn.sub.0.1                                                                              3.38 SnCl.sub.2.2H.sub.2 O                        27   "       "    Te.sub.0.1.Sn.sub.0.1                                                                   3.38 SnCl.sub.2.2H.sub.2 O                                                    4.04 TeCl.sub.4                                   28   "       "    Cr.sub.0.1                                                                              1.50 CrO.sub.2                                    29   "       "    Ni.sub.0.1                                                                              1.78 NiCO.sub.2                                   30   "       "    Ti.sub.0.1                                                                              1.20 TiO.sub.2                                    31   "       "    W.sub.0.1 3.75 H.sub.2 WO.sub.4                             32   "       "    Fe.sub.0.05                                                                             2.02 FeCl.sub.2                                   33   "       "    Te.sub.0.1 Fe.sub.0.05                                                                  4.04 TeCl.sub.4.2.02 FeCl.sub.2                   34   "       "    U.sub.1   137 g heat treated USb.sub.2 O.sub.10             35   "       "    P.sub.0.1 1.73 H.sub.3 PO.sub.4 (85% soln.)                 36   "       "    Te.sub.0.1                                                                              4.041 TeCl.sub.4                                  37   "       "    --        same as in Example 2                              38   "       "    Te.sub.0.1                                                                              4.041 TeCl.sub.4                                  39   "       "    --        same as in Example 2                              40   "       "    P.sub.0.1 1.73 g H.sub.3 PO.sub.4 (85%                      __________________________________________________________________________                                soln.)                                        

The effectiveness of the catalyst of this invention for the conversionof olefins to the corresponding unsaturated aldehydes, acids andnitriles is demonstrated by the conversion of isobutylene tomethacrolein, methacrylic acid and methacrylonitrile, and propylene toacrolein, and acrylic acid shown in the examples in Tables 2 to 5. Theexamples in Table 2 illustrate the improvement obtained in theconversion of isobutylene to methacrolein with the promoted, reduced,antimony-molybdenum catalysts as compared with the unpromoted catalystsfor this same reaction. The data in this Table also show the effect ofvarying the concentration of the promoter, the use of more than onepromoter in the catalyst, and the effect of varying the reactionconditions such as the inclusion of water in the feed. The examplesgiven in Tables 3 to 5 show the effect of these catalysts for theoxidation of other feeds such as propylene and methacrolein to acroleinand methacrylic acid, respectively, and the ammoxidation of isobutyleneto methacrylonitrile.

                                      TABLE II                                    __________________________________________________________________________    Oxidation of Isobutylene to Methacrolein                                      Reaction Conditions                                                           Molar Feed Ratio, IC.sub.4.sup.= /air 1/20                                    Contact Time 3 seconds                                                        Temperature, °C. = 371                                                                      Mole Percent Conversion to:                                                                 Mole Percent                                                           Methacrylic                                                                          Selectivity to                             Example                                                                            Catalyst        Methacrolein                                                                         Acid   Methacrolein                               __________________________________________________________________________    1    Sb.sub.2 Mo.sub.3 O.sub.x                                                                     35.6   --     57                                         2    Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 ° 37.9                                          3.0   61                                                3    Sb.sub.2 Mo.sub.3 O.sub.x + Al.sub.0.06 °                                              44.2   1.2    54                                         4    Sb.sub.2 Mo.sub.3 O.sub.x + Ni.sub.0.06 °                                              43.9   1.0    59                                         5    Sb.sub.2 Mo.sub.3 O.sub.x + S.sub.0.04 °                                               42.9   2.9    65                                         6    Sb.sub.2 Mo.sub.3 O.sub.x + W.sub.0.06                                                        37.6   4.4    42                                         7    Bi.sub.0.01 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                tr     tr     --                                              (HNO.sub.3 was used during the                                                preparation)                                                             8    Bi.sub.0.1 [Sb.sub.2 MoO.sub.x O.sub.x + Mo.sub.0.06                                          44.2ree.]                                                                            tr     62                                         9    Bi.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.04 °]                                 53.4   1.9    63                                              (Nitrate free)                                                           10   P.sub.0.01 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 48.4   1.8    57                                         11   P.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                  30.3   12.1   42                                         12   P.sub.0.25 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 17.6   tr     68                                         13   P.sub.0.5 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                  19.9   0.5    50                                         14   P.sub.1.0 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                   6.8   0.3    30                                         15   B.sub.0.01 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 57.2   2.2    60                                         16   Te.sub.0.01 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                63.5   --     80                                         17   Te.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 71.7   --     77                                         18   Te.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + W.sub.0.06 °]                                  62.2   7.2    74                                         19   Te.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + W.sub.0.2 °]                                   49.1   5.1    55                                         20   W.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                  58.2   --     60                                         21   Mn.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 56.5   0.3    74                                         22   Ni.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 56.5   0.7    70                                         23   Cu.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 56.4   --     70                                         24   Pb.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 55.5   1.2    69                                         25   Re.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 46.1   --     48                                         26   Sn.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 42.4   6.4    53                                         27   Te.sub.0.1 Sn.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub. x + Mo.sub.0.06               °]       77.9   --     85                                         28   Cr.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 41.2   tr     52                                         *29  Ni.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 62.5   1.3    73                                         *30  Ti.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 61.2   3.9    70                                         *31  W.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                  60.6   3.8    70                                         32   Fe.sub.0.5 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                 41.4   tr     46                                         33   Te.sub.0.1 Fe.sub.0.05 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06               °]       60.1                                                     34   U.sub.1 [Sb.sub.4.67 Mo.sub.2.3 + Mo.sub.0.06 ]                                               55.0   4.3    59                                         __________________________________________________________________________     *Molar Feed ratio, IC.sub.4.sup.= /air/H.sub.2 O = 1/11/4                     Reaction Temp., °C. = 399                                         

                                      TABLE III                                   __________________________________________________________________________    Oxidation of Propylene to Acrolein                                            Reaction Conditions                                                           Molar Feed Ratio, C.sub.3.sup.= /air = 1/20                                                     Reaction               Mole Percent                                           Temp.                                                                              C.T.                                                                              Mole Percent Conversion to:                                                                 Selectivity to                       Example                                                                            Catalyst     (°C.)                                                                       (Secs)                                                                            Acrolein                                                                            Acrylic Acid                                                                          Acrolein                             __________________________________________________________________________    35   P.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                               400  3.0 20.7  --      66                                   36   Te.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                              450  5.0 42.5  7.9     84                                   __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________    Ammoxidation of Isobutylene to Methacrylonitrile                              Reaction Conditions                                                           Molar Feed Ratio, IC.sub.4.sup.= /NH.sub.3 /air = 1/1.5/20                    Contact time = 3 seconds.sup.2                                                Temperature, °C. = 399                                                                    Mole Percent Conversion to:                                                                   Mole Percent                                                           Acrolein &                                                                           Selectivity to                             Example                                                                            Catalyst      Methacrylonitrile                                                                      Methacrolein                                                                         Methacrylonitrile                          __________________________________________________________________________    37   [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                          42.5     1.9    43                                         38   Te.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                               71.1     3.5    73                                         __________________________________________________________________________

                                      TABLE V                                     __________________________________________________________________________    Oxidation of Methacrolein to Methacrylic Acid                                 Reaction Conditions                                                           Molar Feed Ratio, Methacrolein/Air/H.sub.2 O = 1/6/5                          Contact Time, sec. = 1.0                                                      Temperature, °C. = 400                                                                   Mole Percent conversion to:                                                                 Mole Selectivity to                           Example                                                                            Catalyst     Methacrylic Acid                                                                            Methacrylic Acid                              __________________________________________________________________________    39   [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                                         11.9          57                                            40   P.sub.0.1 [Sb.sub.2 Mo.sub.3 O.sub.x + Mo.sub.0.06 °]                               25.6          53                                            __________________________________________________________________________

We claim:
 1. A process for the oxidation of propylene and isobutylene toform the corresponding unsaturated aldehydes and unsaturated acidscomprising contacting in the vapor phase at a temperature within therange of from about 250° to about 600° C. a mixture of a molecularoxygen-containing gas and either propylene or isobutylene, or mixturesthereof, in a molar ratio of oxygen to olefin within the range fromabout 0.5 to 10, in the presence of a promoted, reduced, antimonyoxide-molybdenum oxide-containing catalyst wherein the catalyst isprepared by combining the following components in any order:a. anaqueous slurry of molybdenum trioxide; b. a reducing agent selected fromthe group consisting of finely divided metal, sulfur, sulfur dioxide,hydrogen sulfide, hydrazine, hydrate, ammonia, hydroxylamine and anorganic reducing agent capable of reducing at least some of themolybdenum to a valence state below +6 in a ratio of from about 0.0001to 0.2 moles of the reducing agent per mole of molybdenum; c. antimonyoxide in a ratio of from about 0.1 to 9 moles of antimony oxide per moleof molybdenum; and d. at least one promoter element in the form of anon-oxidizing compound selected from the group consisting of tellurium,tungsten, titanium, manganese, nickel, iron, copper, lead, rhenium,bismuth, tin, uranium, chromium, phosphorus and boron, said promoterelement being added in a ratio of from about 0.0001 to 10 moles ofpromoter element per mole of molybdenum.
 2. The process in claim 1wherein the finely divided metal in component (b) in the catalystpreparation is selected from the group consisting of molybdenum,tungsten, aluminum and nickel.
 3. The process in claim 2 wherein thecatalyst components are combined in the following order:a. molybdenumtrioxide is reacted with the reducing agent; b. antimony trioxide isadded to the reaction mixture of (a); and c. the promoter element in theform of a non-oxidizing compound is subsequently added to the reactionmixture of (b). .Iadd.
 4. A process for the production of methacrylicacid by the oxidation of methacrolein with molecular oxygen in the vaporphase at a reaction temperature of about 200° C. to about 500° C. in thepresence of a promoted, reduced, antimony oxide-molybdenum oxidecontaining catalyst wherein the catalyst is prepared by combining thefollowing components in any order: a. an aqueous slurry of molybdenumtrioxide; b. a reducing agent selected from the group consisting of afinely divided metal, sulfur, sulfur dioxide, hydrogen sulfide,hydrazine hydrate, ammonia, hydroxylamine, and an organic reducing agentcapable of reducing at least some of the molybdenum to a valence statebelow +6 in a ratio of from about 0.0001 to 0.2 mole of the reducing permole of molybdenum; c. antimony oxide in a ratio of from about 0.01 to 9moles of antimony oxide per mole of molybdenum; and d. at least onepromoter element in the form of a non-oxidizing compound selected fromthe group consisting of tellurium, tungsten, titanium, manganese,nickel, iron, cobalt, lead, rhenium, bismuth, tin, uranium, chromium,phosphorus and boron, said promoter element being added in a ratio offrom about 0.0001 to 1.0 moles of promoter element per mole ofmolybdenum. .Iaddend..Iadd.
 5. The process of claim 4 wherein the finelydivided metal in component (b) in the catalyst preparation is selectedfrom the group consisting of molybdenum, tungsten, aluminum and nickel..Iaddend. .Iadd.
 6. The process of claim 5 wherein the promoter elementis phosphorus. .Iaddend..Iadd.
 7. The process of claim 6 whereincatalyst is of the formula P₀.01 [Sb₂ Mo₃ O_(x) +Mo°₀.06 ]..Iaddend..Iadd.
 8. The process of claim 5 wherein the finely dividedmetal in component (b) in the catalyst preparation is molybdenum..Iaddend..Iadd.
 9. The process of claim 5 wherein the catalystcomponents are combined in the following order: a. molybdenum trioxideis reacted with a reducing agent; b. antimony trioxide is added to thereaction mixture of (a); and c. the promoter element in the form of anon-oxidizing compound is subsequently added to the reaction mixture of(b). .Iaddend..Iadd.
 10. A process for the production of methacrylicacid by the oxidation of methacrolein with molecular oxygen in the vaporphase at a reaction temperature of about 200° C. to about 500° C. in thepresence of a reduced, antimony oxide-molybdenum oxide containingcatalyst wherein the catalyst is prepared by combining the followingcomponents in any order: a. an aqueous slurry of molybdenum trioxide; b.a reducing agent selected from the group consisting of a finely dividedmetal, sulfur, sulfur dioxide, hydrogen sulfide, hydrazine hydrate,ammonia, hydroxylamine and an organic reducing agent capable of reducingat least some of the molybdenum to a valence state below +6 at ratio offrom about 0.0001 to 0.2 moles of the reducing agent per mole ofmolybdenum; and c. antimony oxide in a ratio of from about 0.1 to 9moles of antimony oxide promoted molybdenum. .Iaddend..Iadd.
 11. Theprocess of claim 10 wherein the finely divided metal in component (b) inthe catalyst preparation is selected from the group consisting ofmolybdenum, tungsten, aluminum and nickel. .Iaddend..Iadd.
 12. Theprocess of claim 11 wherein the finely divided metal in component (b) inthe catalyst preparation is molybdenum. .Iaddend..Iadd.
 13. The processof claim 11 wherein the catalyst is of the formula [Sb₂ Mo₃ O_(x)+Mo°₀.06 ]. .Iaddend. .Iadd.
 14. The process of claim 11 wherein thecatalyst components are combined in the following order:a. molybdenumtrioxide is reacted with the reducing agent; and b. antimony trioxide isadded to the reaction mixture of (a). .Iaddend.